Bis(chloro-bromovinyl sulfoxides)



United States Patent 3 Claims ABSTRACT OF THE DISCLOSURE Compoundshaving the formulae are prepared where at least two of the X groups arechlorine or bromine, two of R R and R are chlorine or bromine and threeof R R R and R are chlorine or bromine and the remaining X and R groupsare hydrogen and Q is nothing or oxygen. The compounds are useful asnematocides and fungicides.

This application is a division of our application Ser. No. 340,504,filed J an. 27, 1964.

This invention relates to new compounds, pesticidal uses of compoundsand new processes of making compounds.

Compounds which have good pre-emergent herbicide activity normally arenot satisfactory as nematocides since there remains the problem ofgrowing crops after the killing of the nematodes.

It is an object of the present invention to prepare nematocides whichare not good pre-emergent herbicides.

Another object is to prepare novel sulfides.

An additional object is to prepare novel unsaturated sulfoxides.

A further object is to prepare mixed saturated-unsaturated sulfoxidesand sulfides.

Yet another object is to devise a novel method for preparing puresulfides.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by the diversemeans as set forth below.

It may be noted that it is not predictable which sulfides and sulfoxideswill have good nematocidal and/or fungicidal activity. Thus,bis(l,2,2,2-tetrachloroethyl) sulfoxide is ineffective as a nematocide.Similarly, bis- (l,2,2,2-tetrachloroethyl) sulfide is completelyineffective as a nematocide and has poor fungicidal activity. Likewise,bis(1,2,2-trichlorovinyl) sulfide shows no nematocidal'activity and poorfungicidal activity. These compounds are not included in the presentinvention. However, somewhat similar compounds structurally, but withinthe invention, have good nematocidal activity and, in some cases, alsohave found good fungicidal activity.

In one aspect of the invention there is prepared bis-(1,2,2-trichloroethyl) sulfide. This compound is a much 3,428,687Patented Feb. 18, 1969 better parasitic nematocide and fungicide thanthe corresponding bis(2,2,2-trichloroethyl) sulfide.

In another aspect of the invention there are prepared unsaturatedsulfoxides of the formula Where at least two of the Xs are halogen ofatomic weight between 35 and 80, i.e., chlorine or bromine, and theother X is a halogen of atomic weight between 35 and or is hydrogen. Ithas been found that the bis(2,2-dihalovinyl) sulfoxides are much poorernematocides than either the bis(l,2-dihalovinyl) sulfoxides or thebis(l,2,2- trihalovinyl) sulfoxides. The bis(l,2,2-trihalovinyl)sulfoxides are poorer fungicides than the corresponding bis-(l,2-dihalovinyl) sulfoxides. Illustrative of such unsaturatedsulfoxides are bis( 1,2-dichlorovinyl) sulfoxide, bis-(2,2-dichlorovinyl) sulfoxide, bis(1,2,2-trichlorovinyl) sulfoxide, bis1,2-dibromovinyl) sulfoxide.

It has been found that mixed trihaloethyl-dihalovinyl sulfides can beobtained by dehydrochlorination of bis- (trihaloethyl) sulfides in thepresence of tertiary amines, e.g., trimethyl amine, triethyl amine,tripropyl amine, triisopropyl amine, tributyl amine, trioctyl amine,pyridine, dimethyl aniline, dipropyl butyl amine, tribenzyl amine. Themixed polyhaloethyl-polyhalovinyl sulfide is obtained even if twice asmuch tertiary amine is used as is theoretically required for thereaction. On the other hand, when other alkaline agents are employed,e.g., alkali metal ethoxides such as sodium methoxide, sodium ethoxideand potassium butoxide, to dehydrochlorinate bis(polyhaloethyl) sulfidesthere are obtained the expected bis(polyhalovinyl) sulfides. Thepolyhaloethyl polyhalovinyl sulfides and the his (polyhalovinyl)sulfides can be converted to the corresponding sulfoxides by oxidation,e.g., with hydrogen peroxide or an organic peroxide. Examples of suchsulfides and sulfoxides not previously mentioned are1,2,2-trichloroethyl-1,2-dich1orovinyl sulfide,1,2,2-trichloroethyl-1,2-dichlorovinyl sulfoxide, 1,2- d-ichlorovinylsulfide, 1,2,2-tribromoethy1-1,2-dibromovinyl sulfide.

The unsaturated sulfoxides can also be formed by directdehydrochlorination of the saturated sulfoxides, e.g., with sodiumalkoxide such as sodium ethoxide.

It is difiicult to prepare pure bis(polyhaloethyl) sulfides, e.g.,bis(1,2,2-trichloroethyl) sulfide or bis(2,2,2- trichloroethyl) sulfidedirectly since the normal procedure for preparing such compounds, e.g.,by reacting SCl with dichloroethylene results in a crudesulfide-disulfide mixture that is difiicult to separate. However, it hasbeen found that if the crude mixture is oxidized to form the sulfoxidethat the latter can be readily separated from the oxidation products ofthe disulfide. The sulfoxide in pure form can then be reduced, e.g.,with TiCl to form the pure bis(polyhaloethyl) sulfide.

Unless otherwise stated, all parts and percentages are by weight.

EXAMPLE 1 In 800 parts (8.0 moles) of symmetric cis dichloroethylenethere were suspended 10 parts of anhydrous ferric chloride and 204 parts(2.0 mole) of sulfur dichloride were added -at 30 to 35 C. over a periodof 3.0 hours. The product was allowed to stand overnight and the ferricchloride removed by filtration. The material was washed with diluteaqueous hydrochloric acid and the organic layer dried and the solventremoved by stripping to give 383 parts of a crude mixture of bis(l,2,2-trichloroethyl) sulfide and disulfide. Upon distillation in a highvacuum there was obtained 60.8 parts (22.2% yield) of purebis(1,2,2-trichloroethyl) sulfide as a yellow oil BR 102 to 108 C., a1.5705.

This example was repeated several times using cis, trans or a mixture ofcis and trans dichloroethylene and reaction times from 2.5 to 3.0 hours.Removal of ferric chloride was also obtained by treatment twice with 1volume of acetone followed by dilution with 2 volumes of water followedby drying. The yields of crude mixtures ranged from 65 to 96% and theyield of pure bis(1,2,2-trichloroethyl) sulfide ranged from 22 to 28%.The pure compound is identified hereinafter as Compound 4975.

EXAMPLE 2 1 part of aluminum chloride was suspended in 50 parts (0.5mole) of cis-dichloroethylene and 20 parts (0.1 mole) of1,2,2-trichloroethyl sulfenyl chloride were added dropwise at 57 C. overa period of 15 minutes. Further heating of the mixture for 1 hour at 60C. completed the reaction. The aluminum chloride catalyst was removed bytreatment with 1 volume of acetone and then 2 volumes of water, theorganic layer dried and then freed of solvent by vacuum stripping. 24.5grams of crude addition product was obtained as a brown oil, n 1.5770.Distillation in a high vacuum gave 15.7 parts (53% yield) ofbis(1,2,2-trichloroethyl) sulfide as a yellow oil B.P. 110 C., n 1.5736having the same basic infrared spectrum as the product of Example 1. Theprocedure of Example 2 gave higher yields, e.g., 47 to 74.0% overseveral different runs, than that of Example 1. However, the products ofExample 2, on the average, were not as pure as those of Example 1.

EXAMPLE 3 Into a suspension of 1 part of ferric chloride in 30 parts ofcis 1,2-dichloroethylene there were added dropwise with stirring 12parts (0.06 mole) of 1,2,2-triehloroethyl sulfenyl chloride at 60 C.(moderate reflux) over a period of 15 minutes. Standing overnight,removing ferric chloride by using acetone and water, drying of theremaining solution and removing the organic solvent in vacuum gave 16.3parts of crude product which, in turn, furnished 7.6 parts (42.5% yield)of pure bis(1,2,2-trichloroethyl) sulfide as a yellow oil, B.P. 125 C.,11 1.5710 when subjected to fractionation in high vacuum.

EXAMPLE 4 3.1 grams (0.01 mole) of bis(1,2,2-trichloroethyl) sulfoxide(prepared in Example 6) were taken up in a mixture of 20 ml. of glacialacetic acid and 20 ml. of acetic anhydride and reduced by dropwiseaddition under stirring of 15 ml. of a 20% TiCl solution in concentratedhydrochloric acid at room temperature with occasional cooling to controlthe exothermic temperature rise over a period of 30 minutes. The mixturewas then kept for 3 hours at 90 to 95 C. and allowed to stand overnightat room temperature. All operations were carried out in a nitrogenatmosphere. Filtering off the formed precipitate of titanium dioxide andoxychlorides, diluting the filtrate with 2 volumes of water, taking upthe heavy oil into chloroform, repeated washing free of acid with water,drying and stripping of the solvent gave 2.8 grams (94% yield) of crudebis(1,2,2-trichloroethyl) sulfide, most of which distilled at 90 to 95C. at 0.05 mm. Hg and having the same basic infrared spectrum as theproduct of Example 1.

EXAMPLE Into 100 parts of a crude mixture of bis(1,2,2-trichloroethyl)sulfide and bis(1,2,2-trich1oroethyl) disulfide made as in Example 1there were introduced under stirring and occasional cooling by means ofan external ice-water bath at 30 C. over a period of 1 hour parts of drychlorine gas, suflicient to convert the 70% disulfide in the crudemixture to easily distillable 1,2,2-trichloroethyl sulfenyl chloride.The resulting mixture was then subjected to flash evaporation at 0.1 mm.Hg. The sulfenyl chloride which came over at 30 to 40 C. was recoveredby trapping and the residue distilled in a high vacuum to give 17 partsof bis(1,2,2-t1ichloroethyl) sulfide as a yellow oil in a yield of 57%.In other runs yields up to 63% were obtained.

EXAMPLE 6 62 grams (0.209 mole) of redistilled bis(1,2,2-trichloroethyl)sulfide were oxidized by diluting with ml. of glacial acetic acid andgradually mixing with 23.7 grams of 30% aqueous hydrogen peroxide (aslight excess) followed by standing at room temperature (25 C.) over aperiod of 42 hours, followed by heating at 60 to 70 C. for a further 2hours. Diluting with 2 volumes of water, taking up the precipitated oilinto chloroform, removing free acetic acid by repeated washing withwater, drying and stripping of the solvent furnished a yield of 55 grams(84% yield) of a heavy oil which, on diluting with petroleum ether(Skelly B) and repeated cooling, gave 21 grams (32% yield) of crudesolid product which was recrystallized to give 17 grams (26% yield) ofpure white crystals of bis(1,2,2-trichloroethyl) sulfoxide, M.P. 88 C.,B.P. 102 to 105 C., Cl 67.0% (68.0% theory); S 10.0% (theory 10.2%). Thepure solid product is identified hereinafter as Compound 4922.

In a repeat of this experiment using a 4 day standing period at roomtemperature for the oxidation the yield of pure product was increased to34%. Low temperatures were also found to diminish the formation ofunsaturated materials as impurities.

EXAMPLE 7 60 grams (0.202 mole) of pure bis(1,2,2-trichloroethyl)sulfide were diluted with 150 ml. of glacial acetic acid, 20.2 grams of30% aqueous hydrogen peroxide were added and the mixture allowed tostand for 4 days at room temperature (25 to 27 C.). The mixture waspoured into 2 volumes of ice-water, the bottom oil taken up withchloroform and this solution treated as described in Example 6 to give63.5 grams (quantitative yield) of crude oil, from which after removalof the solid bis(1,2,2- trichloroethyl) sulfoxide by chilling from thepetroleum ether (Skelly B) and vacuum stripping gave 34.2 grams (54%yield) of bis(1,2,2-trichloroethyl) sulfoxide-oil form (i.e., theoil-modification). This was subjected to high vacuum distillation andboiled 117 to 125 C. at 0.02 to 0.03 mm. Hg and had an 11 1.5602 to1.5720. About 10 grams of the last fraction obtained in this range hadan n 1.5720 and was a thick, almost colorless syrup. The oil product wasthus divided into two fractions. The lower boiling fraction in the 117to 125 C. range analyzed Cl 66.3%, S 10.6% and the higher boilingfraction in the 117 to 125 C. range analyzed Cl 66.8%, S 11.6%. (Theoryfor bis(1,2,2-trichloroethyl) sulfoxide is CI 68.0%, S 10.2%.) Theinfrared spectrum for the high boiling oil fraction in Example 7 wasvery similar to that of the solid product of Example 6 both showingpeaks at 3.4 microns, 7.8 microns, 9.3 microns, 9.8 microns, 12.6microns and 13.7 microns. The spectrum for the solid product of Example6 showed a trace of unsaturated impurity at 10.9 microns while thespectrum of the oil of Example 7 showed considerably more unsaturatedimpurity at 10.9 micron and also showed unsaturated impurities at 6.4microns. The high boiling fraction in Example 7 was redistilled and hada B.P. to 117 C. This oil-modification of bis(1,2,2-trichloroethyl)sulfoxide is identified hereinafter as Compound 5008.

Crystallization of the oil-modification of bis(1,2,2-trichloroethyl)sulfoxide prepared in Example 7 could not be achieved in this experimentor in a repeat experiment in which 51% yield of the oil-modification wasobtained.

EXAMPLE 8 10 grams of ferric chloride (anhydrous) were suspended in 400grams (100% excess) of vinylidene chloride and 102 grams (1.0 mole) ofsulfur dichloride were added dropwise under stirring and occasionalcooling to maintain a gentle reflux (35 C.) over a period of V 1 hour.Standing overnight, heating to reflux for 3 hours, removing ferricchloride by treatment with acetone, drying and stripping off excessvinylidene chloride gave 232 grams of crude bis(2,2,2-trichloroethyl)sulfide-bis(2,2,2- trichloroethyl) disulfide mixture which was subjectedto fractionation. A 30% yield was obtained of a colorless fraction whichhad a B.P. 91 C., 11 1.5642. This was redistilled to give purebis(2,2,2-trichloroethyl) sulfide (Compound 5006) B.P. 88 to 89 C., n1.5551. The product solidified on standing to white needles M.P. 45 C.

EXAMPLE 9 3.5 grams (0.0118 mole) of bis(2,2,2-trichloroethyl) sulfidewere diluted with 10 m1. of glacial acetic acid and 1.2 grams of 31.0%aqueous hydrogen peroxide (0.01) mole added. The mixture was allowed tostand for 6 days at room temperature to C.) and diluted with Water togive 3.7 grams (quantitative yield) of the crude product as a whitesolid. The latter was taken up in chloroform, washed several times withwater, dried and stripped to give 1.8 grams (50% yield) ofbis(2,2,2-trichloroethyl) sulfoxide (Compound 5025) as a white solidwhich on recrystallization had a M.P. of

13s" to 137 0. and had a B.P.0 09 of 143 to 144 0.

EXAMPLE 10 29.7 grams (0.1 mole) of bis(1,2,2-trichloroethyl) sulfidewere diluted with 100 ml. of petroleum ether (Skelley B) anddehydrochlorinated by dropwise addition with stiring and occasionalcooling of 20.3 grams (0.2 mole) of triethyl amine in Skelley B (1:1 byvolume). Continued stirring at room temperature for 4 hours, removingthe triethylamine hydrochloride formed and the unreacted triethylamineby washing with dilute aqueous hydrochloric acid and then with diluteaqueous sodium bicarbonate, followed by drying and stripping off thesolvent gave 24 grams (quantitative yield) of crude residue which ondistillation gave 20.5 grams (85% yield) of1,2-dichlorovinyl-1,2,2-trichloroethyl sulfide (Compound 4968) as ayellow oil B.P. 53 to 54 C., n 1.5715 which analyed Cl 66.6% (theory68.2%), S 11.7% (theory 12.3%).

EXAMPLE 11 10 grams (0.0336 mole) of bis(1,2,2-trichloroethyl) sulfidewere dissolved in 50 ml. of anhydrous benzene and a solution of 1.55grams of sodium metal (2 gram equivalents) in 100 ml. of anhydrous ethylalcohol was added dropwise with stirring at 20 to 25 C. with occasionalcooling. The dehydrochlorination proceeded rapidly and the sodiumchloride formed in quantitative amount was filtered off after thereaction mixture was stirred for 1 hour at room temperature (25 to 30C.). Removal of all the solvents gave 7.3 grams (97% yield) of crudebis- (1,2-dichlorovinyl) sulfied as a yellow oil which, afterdistillation, gave 5.5 grams (73% yield) of pure bis(l,2- dichlorovinyl)sulfide (Compound 5021) as a yellow oil B-P-0 o3 to 43 C. "D28 EXAMPLE12 5 grams (0.0208 mole) of recrystallized bis(1,2-dichlorovinyl)sulfoxide prepared according to Example 13 were dissolved in a mixtureof 20 ml. of glacial acetic acid and 25 ml. of acetic anhydride andreduced by dropwise addition with stirring of 30 ml. of a 20% solutionof TiCl in concentrated hydrochloric acid. The mixture was kept for 4hours at 95 to 100 C. All of the operations were car ried out in anitrogen atmosphere. The titanium oxide and oxychlorides formed werefiltered off, the filtrate was diluted with 2 volumes of water, and theoil taken up in chloroform, repeatedly washed with water until free ofacid, dried and stripped of solvent to give 2.5 grams (54% yield) ofbis(1,2-dichlorovinyl) sulfide as a yellow oil B.P.0 04, 40 to 41 0.,"D20 EXAMPLE 13 12 grams (0.0383 mole) of pure bis(1,2,2-trichloroethyl)sulfoxide were dissolved in 100 ml. of dry benzene anddehydrochlorinated by dropwise addition with stirring and cooling atbetween 4 and 10 C. of a solution of 7.75 grams (0.0766 mole) oftriethylamine in 50 ml, of dry benzene over a period of 1 hour. Themixture was allowed to warm to room temperature with continued agitationover a period of 1 further hour, the triethylamine hydrochloride formedwas removed, the product washed first with dilute hydrochloric acid andthen with water until neutral, dried and the benzene removed in vacuumto give 8.1 grams (88.2% yield) of crude product which was distilled togive 7 grams (76% yield) of bis(1,2-dichlorovinyl) sulfoxide (Compound4965) as a colorless oil B.P. 69 to 70 C., n 1.5865. The oil solidifiedon standing. It was recrystallized from Skelley B to give 5.3 grams(57.5% yield) of pure Compound 4965, M.P. 58 C. Analysis gave for C157.5% (theory 59.2%) and for S 13.2% (theory 13.4%

EXAMPLE 14 1.5 grams (0.0067 mole) of bis(1,2-dichlorovinyl) sulfidewere diluted with 15 ml. of glacial acetic acid and mixed with 0.76 gramf0 30% aqueous hydrogen peroxide. The reaction mixture was allowed tostand at room temperature (25 to 27 C.) for two days, poured into waterand small amounts of acetic acid and water were removed from the bottomoil obtained to give 1.6 grams (quantitative yield) of a colorless oilwhich solidified on standing. The product was bis(l,2-dichlorovinyl)sulfoxide. It had the same infrared spectrum as the product of Example13.

EXAMPLE 15 13.0 gram (0.05 mole) of1,2-dichlorovinyl-1,2,2-trichloroethyl sulfide were diluted with 30 ml.of glacial acetic acid and slowly mixed with 5.9 ml. of a 30% aqueoushydrogen peroxide solution and allowed to stand at room temperature for48 hours. The oxidation was completed by heating for 45 minutes at C,The mixture was poured into two volumes of water, the bottom oil takenup in chloroform, washed free of acetic acid with water, dried andstripped to give 12.7 grams (92% yield) of crude product which wasdistilled to give 9.5 grams of pure 1,2 dichlorovinyl1,2,2-trichloroethyl sulfoxide (Compound 5009) B.P. 87 to 89 C., n1.5765. Elemental analysis gave for C1 62.9% (theory 64.1%) and for S10.9% (theory 1.6%

EXAMPLE 16 10 grams (0.032 mole) of purebis(2,2,2-trichororethyl)sulfoxide made according to Example 9 weredissolved in a mixture of 25 ml. of acetic acid and 35 ml. of aceticanhydride. Then, 40 ml. of a 20% TiCl solution in concentratedhydrochloric acid were added with care under stirring and cooling.Finally, the temperature was allowed to go up to to C. and kept therefor 6 hours. The process was carried out in a nitrogen atmosphere. Theproduct was then purified in the manner described in Example 4 anddistilled to give 5 grams (53%) of bis(2,2,2-trichloroethyl) sulfideB.P. 88 to 89 C., n 1.5551.

EXAMPLE 17 To 60 grams of bis(2,2,2-trichloroethyl) sulfide-bis-(2,2,2-trichloroethyl) disulfide mixture (0.2 molar as the sulfide)diluted with 100 ml. of glacial acetic acid there were added 52.3 gramsof a 26% aqueous hydrogen peroxide solution (0.4 mole) at 90 to 105 C.over a period of 1 hour with stirring. The mixture was heated 7 furtherfor 1 hour at 93 C. and then allowed to stand overnight at roomtemperature to complete the oxidation. The mixture was diluted with 2volumes of water, filtered, washed free of acids, taken up inchloroform, dried and stripped to give 15 (24% yield) of crude solidwhich was recrystallized from Skelly B to give 13 grams (21% yield) ofpure bis(2,2,2-trichloroethyl) sulfoxide, M.P. 136 to 137 C. (Compound5025). Elemental analysis gave for C1 6 6.6% (theory 68.0%) and for S9.9% (theory 10.2%).

EXAMPLE 1 8 To 6.0 grams (0.025) mole) of bis-(2,2-dichlorovinyl)sulfoxide (Compound 5026) diluted with a mixture of 15 ml. of glacialacetic acid and 35 ml. of acetic anhydride there were added dropwisewith stirring 30 grams (0.05 mole) of a 20% TiCl solution inconcentrated hydrochloric acid while cooling under a blanket of nitrogengas. The temperature was allowed to rise slowly to 100 to 105 C. by theend of the addition period. The mixture was kept at this temperature for3 hours and then worked up and the crude product isolated in the mannerdescribed in Example 4. The product was distilled in a high vacuum togive 4.0 grams (77% yield) of pure bis(2,2-dichlorovinyl) sulfide(Compound 5027), B.P. 59 to 60 C., r1 1.5955. Elemental analysis gavefor C1 61.7% (theory 63.3%) and for S 14.3% (theory 141%).

EXAMPLE 19 10 grams (0.0336 mole) of bis(2,2,2-trichloroethyl) sulfidewere dissolved in 50ml. of anhydrous benzene and dehydrochlorinated bydropwise addition with stirring and occasional cooling of -100 n11. ofanhydrous ethyl alcohol containing 1.55 grams (2 gram equivalents) ofsodum metal at 20 to 25 C. The mixture was allowed to stand at roomtemperature for 5 to 6 hours, the sodium chloride formed filtered off,the product washed with water, extracted with chloroform, dried and thesolvents removed by distillation to give 3.0 grams (40% yield) of purebis(2,2-dichlorovinyl) sulfide, B.P. 47 C., 11 1.5'872.

EXAMPLE 20 6.5 grams (0.0219 mole) of bis(2,2,2-trichloroethyl) sulfide(Compound 5006) were diluted with 25 ml. of benzene anddehydrochlorinated by dropwise addition of 4.43 grams (0.0428 mole) oftriethylamine. Standing overnight at room temperature (25 to 30 C.)followed by refluxing for 2 hours, removing the triethylaminehydrochloride and unreacted triethylamine by filtration and washing withdilute aqueous hydrochloric acid and water gave 3.5 grams of a yellowoil, most of which distilled at B.P. 51 to 52 C. and which was a mixtureof a large proportion of 2,2-dichlorovinyl-2,2,2- trichloroethyl sulfide(Compound 5103) with some bis- (2,2-dichlorovinyl)sulfide and somestarting Compound 5006.

EXAMPLE 21 The amount of triethylamine was reduced to only 1 moleequivalent in this example wherein 10 grams (0.0337 mole) ofbis(2,2,2-trichloroethyl) sulfide (Compound 5006) were diluted with 50ml. of Skelly B and 3.4 grams (0.0337 mole) of triethylamine were addeddropwise with stirring at 10 to C. The temperature was allowed to riseto room temperature, followed by refluxing at 55 C. for 3 hours tocomplete the reaction. Washing the resulting Skelly B solution withdilute aqueous hydrochloric acid, sodium bicarbonate and water, followedby drying and stripping and distillation in high vacuum gave 5.4 gramsof a pale orange oil, B.P. 70 to 73 C., 11 1.5575. Infrared analysis andgas chromatorgraphy showed that the product was a mixture of2,2-dichlorovinyl-2,2,2-trichloroethyl sulfide (Compound 5103),bis(2,2-dichlorovinyl) sulfide (Compound 5027) and the starting Compound5006.

Compound 5103 was isolated in pure form by separating from a gaschromatographic column of a sample obtained by using ethyl alcohol asthe solvent during dehydrochlorinatiorl.

Example 21 was repeated by replacing the Skelly B in turn by benzene,tetrahydrofurane and ethyl alcohol and a similar mixture of productsobtained. The general method was to dissolve 10 grams (0.03 mole) ofCompound 5006 in 50 ml. of benzene (or tetrahydrofurane, or ethylalcohol), heating to beginning reflux and adding slowly 3.7 grams (1.1mole equivalent) of triethylamine over 30 minutes, washing the benzenemixture with water, taking up the oil in chloroform, drying andstripping to give crude oils which were separated into their componentsby gas chromatography.

Thus, the results using bis(2,2,2-trichloroethyl) sulfide (Compound5006) using triethylamine as the dehydrochlorination agent are differentfrom those using bis- (1,2,2-trichloroethyl) sulfide (Compound 4975).Compound 4975, even with a considerable excess of triethylamine gave thehemi-unsaturated Compound 4968 exclusively, whereas Compound 5006 gavemixtures of hemi-unsaturated Compound 5103 and considerable amounts ofthe fully unsaturated Compound 5027.

EXAMPLE 22 13.0 grams (0.0415 mole) of bis(2,2,2-trichloroethyl)sulfoxide were dissolved in 75 ml. of dry benzene and dehydrochlorinatedby dropwise addition of 8.4 grams (0.083 mole) of triethylamine withstirring and cooling at 10 to 15 C. for 30 minutes. The mixture wasallowed to warm to room temperature (25 to 30 C.), the triethylaminehydrochloride formed removed by filtration, the product washed withWater, dried and the benzene filtrate stripped to give 9.0 grams (90%yield) of bis(2,2-dichlorovinyl) sulfoxide (Compound 5026) afterchilling of a Skelly B solution of the crude material from the benzenesolution. Compound 5026 was a white crystalline solid, M.P. 35 to 36 C.

EXAMPLE 23 10 grams of anhydrous ferric chloride were dispersed in 786grams (6.0 mole) of trichloroethylene, the mixture warmed to to C. and206 grams (2.0 moles) of sulfur dichloride added at this temperaturedropwise with stirring over a period of 1 hour. The mixture was heatedfor an additional 3 hours at 70 to 75 C. and the ferric chloride removedby filtration, followed by decanting with acetone, drying and strippingto give 526 grams of a mixture of bis(1,2,2-tetrachloroethyl) sulfideand bis(1,2,2,2-tetrachloroethyl) disulfide as a dark oil. This dark oilmixture is identified hereinafter as Compound 4501.

A 102 gram portion of this product was fractionated to give 20 grams ofpure bis(1,2,2,2-tetrach1oroethyl) sulfide (compound 5052), B.P. 74 to75 C.,

EXAMPLE 24 10 grams (0.0273 mole) of Compound 5052 were dissolved in 50ml. of glacial acetic acid and 3.1 grams of 30% aqueous hydrogenperoxide added at room temperature. The oxidation mixture was allowed tostand for 2 weeks, followed by heating at to C. for 3 hours. The mixturewas poured into 1 volume of water, the bottom oil freed of acetic acidby successive water washings, diluted with chloroform and dried overanhydrous magnesium sulfate, and the solvent stripped to give 7.1 grams(70% yield) of bis(1,2,2,2-tetrachloroethyl) sulfoxide (Compound 5054) n1.5830.

EXAMPLE 25 15 grams (0.0408 mole) of bis(1,2,2,2-tetrachloroethyl)sulfide were dissolved in 50 ml. of dry benzene and 9 dehydrochlorinatedby dropwise addition at 30 to 35 C. with stirring and cooling of 4.12grams (0.0816 mole) of triethylamine in 10 ml. of benzene. Stirring ofthe mixture at room temperature for 3 hours followed by standing for 48hours completed the reaction. Filtration and water washing to remove allthe triethylamine hydrochloride, drying and stripping of the benzenesolution gave 12.5 grams of crude residue which furnished 10.0 grams(83.5% yield) of bis(perchlorovinyl) sulfide (Compound 5053) as a yellowoil, B.P. 71 to 73 C., n;{ 1.5985.

EXAMPLE 26 To 5 grams (0.0162 mole) of bis(perchlorovinyl) sulfoxidediluted with 15 ml. of acetic acid and 35 ml. of acetic anhydride therewere added dropwise 20 grams (0.032 mole) of a solution of 20% TiCl inconcentrated hydrochloric acid with stirring and cooling in a nitrogenatmosphere. The temperature was allowed to gradually climb to 100 to 105C. at the end of the addition period. The mixture was heated at 100 to105 C. for a further 3 hours to complete the reduction. The precipitateof titanium oxide and oxychlorides was filtered off, the filtratediluted with 2 volumes of water, taken up in chloroform, washedrepeatedly with water to remove the acid, dried and stripped of solventto obtain 3.5 grams of bis(perchlorovinyl) sulfide.

EXAMPLE 27 13 grams (0.034 mole) of Compound 5054 were dissolved in 100ml. of dry benzene and dehydrochlorinated by dropwise addition of 6.9grams (0.068 mole) of triethylamine diluted with 20 ml. of benzene withstirring at 30 to 35 C. over a period of 20 minutes. Further heating for1 hour at 50 to 60 C., removing the triethylamine hydrochloride byfiltration and washing with diluted aqueous hydrochloric acid, dryingover anhydrous magnesium sulfate gave 10.5 grams (a quantitative yield)of crude product which was found to contain 78% of bis(perchlorovinyl)sulfoxide (Compound 5055), an oil which, on distillation in high vacuum,had a B.P. 95 to 100 C., n 1.6070.

EXAMPLE 28 5 grams (0.0169 mole) of bis(perchlorovinyl) sulfide weretaken up in 20 ml. of glacial acetic acid and 2.0 grams of 30% aqueoushydrogen peroxide solution were added at room temperature. This mixturewas allowed to stand for 14 days, poured into 2 volumes of water, thebottom oil taken up in chloroform, washed repeatedly with water toremove acetic acid, dried and stripped to given 4.6 grams (87% yield) ofcrude bis(perchlorovinyl) sulfoxide n 1.6024, Cl 67.8% (theory 68.9% S10.6% (theory 10.4%

EXAMPLE 29 Even when the amount of peroxide was doubled it was notpossible to form the sulfone from Compound 5053 but, instead, thesulfoxide (Compound 5055) was obtained, as shown in this example.

1.5 grams (0.00512 mole) of bis(perchlorovinyl) sulfide were taken up in15 ml. of glacial acetic acid, 1.10 grams (0.0102 mole) of 30% aqueoushydrogen peroxide added and the mixture heated on a steam bath for 3hours. After standing for several days at room temperature, it wasworked up by pouring into water, the lower oil layer taken up inchloroform, the small amount of acetic acid removed by repeated washingwith water, the product dried and stripped to give 1.3 grams (82% yield)of pure bis(perchlorovinyl sulfoxide as a colorless oil.

The compounds of the present invention can be used alone as nematocidesor fungicides, but it has been found desirable to apply them to thepest, e.g., to the soil habitat of nematodes, together with inert solidsto form dusts, or more preferably suspended in a suitable liquiddiluent, preferably water. There can also be added surface active agentsand inert solids in such liquid formulations. Desirably, 0.05 to 1% byweight of surface active agent is employed. The active ingredient can befrom 0.01 to by weight of the entire composition in such cases.

In place of water there can be employed organic solvents as carriers,e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, dieseloil, fuel oil, and petrolum naphtha, ketones such as acetone, methylethyl ketone and cyclohexanone, and alcohols, e.g., ethanol, isopropanoland amyl alcohol, etc.

The nematocides and fungicides of the present invention can also beapplied with inert nematocidal or fungicidal adjuvants or carriers suchas talc, pyrophyllite, synthetic fine silica, Attaclay, kieselguhr,chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullersearth, cottonseed hulls, wheat flour, soyabean flour, pumic, tripoli,wood flour, walnut shell flour, redwood flour and lignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agents,i.e., wetting agent, are advantageously employed in both the solid andliquid compositions. The surface active agent can be anionc, cationic ornonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkyl sulfiate salts, alkylamide sulfonatesalts, alkylaryl polyether alcohols, fatty acid esters of polyhydricalcohols and the alkylene oxide addition products of such esters, andaddition products of long chain mercaptans and alkylene oxides. Typicalexamples of such surface active agents include the sodium alkyl benzenesulfonates having 14 to 18 carbon atoms in the alkyl group,alkylphenol-ethylene oxide condensation products, e.g., p-isooctylphenolcondensed with 10 ethylene oxide units, soaps, e.g., sodium stearate andpotassium oleate, sodium salt of propylnaphthalene sulfonic acid,(di-2-ethyl hexyl) ester of sodium sulfosuccinic acid, sodium laurylsulfate, sodium salt of the sulfonated monoglyceride of cocoanut fattyacids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride,octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether,polyethylene esters of fatty acids and resin acids, e.g., Ethofat 7 and13, sodium N- methyl-N-oleyltaurate, Turkey Red Oil, sodiumdibutylnaphthalene sulfonate, sodium lignin sulfonate (Marasperse N),polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiarydodecyl polyethylene glycol thioether (Nonionic 218), long chainethylene oxide propylene oxide condensation products, e.g., Pluronic 61,sorbitan monolaurate, polyethylene glycol ester of tall oil acids,sodium octylphenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitanmonostearate (Tween 60), sodium dihexyl sulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional methods. Thus, the active ingredient can be mixed with thesolid carrier in finely divided form in amounts small enough to preservethe free-flowing property of the final dust composition.

In commercial'practice the compositions containing the nematocides ofthe present invention are applied to the soil infested with nematodes.

In the following examples or tables illustrating nematocidal orfungicidal activity the compounds of the invention, as well as thecomparison compounds, were formulated are wettable powders consisting of50% of the compound being tested, 46% Hi-Sil 233 (ultra fine silica), 2%Marasperse N (sodium lignin sulfonate) and 2% Pluronic (polyethyleneoxide-propylene oxide adduct molecular weight about 1000). This wettablepowder is hereinafter designated as Formulation A.

EXAMPLE 30 The saprophytic nematode tests (NESA) were carried out inwater as the medium with Panagrellus and Rhabditis spp. nematodes atroom temperature utilizing Formulation A. The results are recorded inTable I as percent kill at the indicated dosages in parts per millionafter a 4 day incubation period. A 10% kill is merely the same amount ofkill as occurs with a blank sample.

It will be observed that the unsaturated sulfoxide Compound 5055(perchlorovinyl sulfoxide) was an excellent nematocide whereas thecorresponding sulfide (Compound 0 53) was completely ineffective. Bothbis(1, 2,2,2-tetrachloroethyl) sulfide (Compound 5052) and thecorresponding sulfoxide (Compound 5054) were also ineffective asnematocides. In contrast, bis(1,2,2-trichloroethyl) sulfide (Compound4975) and the corresponding sulfoxide (Compounds 4922 and 5008) wereexcellent nematocides. Bis(1,2--dichlorovinyl) sulfide (Compound 5021)was a good nematocide and the corresponding sulfoxide (Compound 4965)was even better. This was also true of the mixed saturated-unsaturatedsulfide Compound 4968 and the corresponding sulfoxide (Compound 5009).

The bis(2,2-dichlorovinyl) sulfide (Compound 50 27) and sulfoxide(Compound 5026) were considerably inferior as nomatocides to thecorresponding 1,2-d-ichlorovinyl isomers (Compounds 5021 and 4965).Surprisingly, in view of the other results his(2,2,2-trichloroethyl)sulfide (Compound 5006) was a better nematocide than the correspondingsulfoxide (Compound 5025), although neither was among the bettercompounds tested.

EXAMPLE 31 Several of the compounds were also tested against parasiticnematodes employing Formulation A. The nematode employed was Meloidogynespp. and the procedure was a day contact test carried out in water-agarmedium in the presence of tomato roots at room temperature. The resultsindicated high activities eJg. for Compounds 4975 and 4922, which werefound to be 100% effective at p.p.m. and 50% eifective at 12.5 p.p.m.rates of application.

EXAMPLE 32 The compounds were also tested as fungicides in platefungicide tests as indicated in Table II. The compounds were made upinto Formulation A and then added to agar cultures of the fungi. In thetable, 10 indicates 100% 12 effectiveness and 0 indicates noefiectiveness. In Table II, P stands for Pythium spp., R forRhizoctonia, F for Fusarium and H for Helminthosporium. Theconcentrations are expressed as parts per million (p.p.m.).

TABLE II P R F Compound at p.p.m.

Compounds 4922, 5008, 4965 and 5009 were very effective as soilfungicides at the rate of (1bs./ acre) of 200, 100, 50, 25 and 12.5.Compounds 5054 and 5055 were eifective soil fungicides at 2 00 and 50 lbs/acre. Compound 4922 was the best of all the compounds as a soilfungicide.

Bis(1,2,2-trichloroethyl) sulfoXide and its use as a fungicide andnematocide are claimed in our copending application Ser. No. 338,297,filed Ian. 17, 1964, now Patent 3,249,495.

What is claimed is:

1. A compound having the formula where at least two of the X groups arehalogen of atomic weight between 35 to 80 and the remaining X isselected from the group consisting of halogen of atomic Weight between35 and 80 and hydrogen.

2. Bis(1,2-dichlorovinyl) sulfoxide.

3. Bis(1,2,2-trichlorovinyl) sulfoxide.

References Cited UNITED STATES PATENTS 3,101,377 8/1963 Bluestone et al.260607 OTHER REFERENCES Ketrov et el.: Chem. Abstracts, vol. 27, p. 952(1933).

CHARLES B. PARKER, Primary Examiner.

D. R. PHILLIPS, Assistant Examiner.

US. Cl. X.R. 2 -609 424335

